Mineral exploration has increasingly targeted areas covered by in situ or transported overburden for shallow to deep-seated orebodies. It remains critical to develop better means to detect the surficial chemical footprint of mineralized areas covered by thick regolith. In such settings, plant geochemistry could potentially be a useful exploration tool, as different plant species have varying degrees of tolerance to metal enrichment in the soil. This review provides insights into the geological and geochemical controls on metal accumulation patterns in soil–plant systems of the Central African Copperbelt. In addition, it highlights the opportunities for integrating the geochemistry of terrestrial plants in emerging exploration technologies, identifies research gaps, and suggests future directions for developing phytogeochemical sampling techniques. This review was conducted using reputable online scholarly databases targeting original research articles published between January 2005 and March 2023, from which selected articles were identified, screened, and used to explore current advances, opportunities, and future directions for the use of plant geochemistry in sediment hosted Cu–Co exploration in the Central African Copperbelt. Various plant species are recognized as ore deposit indicators through either independent phytogeochemistry or complementary approaches. In the Central African Copperbelt, the successful application of hyperaccumulator species for phytoremediation provides the basis for adopting phytogeochemistry in mineral exploration. Furthermore, current advances in remote sensing, machine learning, and deep learning techniques could enable multi-source data integration and allow for the integration of phytogeochemistry.